EP1042218B1 - Process for preparing nanocrystalline metal hydrides - Google Patents

Process for preparing nanocrystalline metal hydrides Download PDF

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EP1042218B1
EP1042218B1 EP98966570A EP98966570A EP1042218B1 EP 1042218 B1 EP1042218 B1 EP 1042218B1 EP 98966570 A EP98966570 A EP 98966570A EP 98966570 A EP98966570 A EP 98966570A EP 1042218 B1 EP1042218 B1 EP 1042218B1
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hydride
powder
mgh
hydrides
elements
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German (de)
French (fr)
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EP1042218A1 (en
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Thomas Klassen
Wolfgang Oelerich
Rüdiger BORMANN
Volker GÜTHER
Robert Schulz
Jacques Huot
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Hydro Quebec
GfE Metalle und Materialien GmbH
Helmholtz Zentrum Geesthacht Zentrum fuer Material und Kustenforschung GmbH
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Hydro Quebec
GfE Metalle und Materialien GmbH
Helmholtz Zentrum Geesthacht Zentrum fuer Material und Kustenforschung GmbH
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/24—Hydrides containing at least two metals; Addition complexes thereof
    • C01B6/243—Hydrides containing at least two metals; Addition complexes thereof containing only hydrogen, aluminium and alkali metals, e.g. Li(AlH4)
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/24—Hydrides containing at least two metals; Addition complexes thereof

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  • the invention relates to a process for the preparation of nanocrystalline metal hydrides.
  • Hydrogen storage so-called hydride storage
  • the storage is charged by heat, ie hydrogen is bound by chemisorption and discharged by supplying heat again.
  • Hydrogen storage could thus form excellent energy storage for mobile and / or stationary applications, ie they would, since the discharge of the hydrogen storage no harmful emissions are released, form a considerable storage potential in the future.
  • nanocrystalline hydrides which are characterized by rapid hydrogen uptake and release kinetics.
  • their production has so far been very expensive.
  • nanocrystalline alloys have been produced by high energy milling from elemental components or master alloys, whereby the grinding times can be very long.
  • these nanocrystalline alloys were u.U. subjected to multi-stage heat treatment under high hydrogen pressure and hydrogenated in this way.
  • many alloys require multiple hydrogen loading and unloading to achieve full capacity.
  • TN Dymove et al Coordination Chemistry, 1993, vol. 19, no. 7, pp. 529-534 discloses the preparation of hydrides of aluminum and alkali metal by mechanical milling of aluminum hydride and alkali metal hydride. The grinding takes place under argon atmosphere.
  • an elemental metal hydride of a first type with at least one elemental metal to provide an alloy hydride are subjected to a mechanical grinding process.
  • the advantage of the solution according to the invention consists essentially in that, as desired, with a high yield up to the range of 100%, a production of stable and metastable hydrides or hydrides of metastable alloys in a relatively simple manner is possible and the disadvantages associated with the In addition, with the process according to the invention, it is also possible to prepare hydrides which can not be prepared at all by means of the known processes.
  • the grinding of the mixture of elemental metal hydride, metal and possibly several other metal hydrides is preferably carried out for a predetermined time, preferably the grinding process is in the range of 20 to 200 hours.
  • the time interval of the milling process of the type of grinder used depends so that the specified, preferably grinding times can be under or exceeded. In general, however, it can be said that the grinding times according to the invention are significantly shorter than those during grinding without the use of hydrides.
  • the grinding process takes place under an inert gas atmosphere.
  • hydrides for example, magnesium iron hydride
  • magnesium iron hydride have been produced by sintering at high temperature and under high hydrogen pressure. It had been tried to stay in this example to grind magnesium and iron in a hydrogen atmosphere, but this did not result in a synthesis of the desired magnesium iron hydride.
  • By grinding magnesium hydride and iron in a certain molar ratio under an inert gas atmosphere it is possible according to the invention to directly synthesize a hydrogen-enriched hydride at the end of the grinding process, which has shown very good results, in particular when using argon as an inert gas.
  • the first elemental metal hydride consists of metals of the 1st or 2nd main group of the Periodic Table of the Elements.
  • the metals are preferably Li, Na, K, Mg, Ca, Sc, Y, Ti, V, Ny or La, which elements are preferably Fe, Co, Nb, Cu, Zn, Al and Si.
  • Particularly good process results were also achieved in that preferably the elemental metal consists of elements of VIII. Subgroup of the Periodic Table of the Elements.
  • the metal hydrides and / or the metal are previously converted into a powdery form and then the powdered metal hydrides and / or the metal are subjected to the grinding process according to the invention.
  • the process is effectively operable and consequently operable with an extremely high yield.
  • MgH 2 powder and elemental Ni powder were mixed in a molar ratio of 2: 1.
  • 40 g of this powder mixture was ground in a planetary ball mill (type Fritsch P5), at 230 revolutions / min, with a hardened chrome steel cup (with a volume of 250 ml) and balls. (with a diameter of 10 mm) were used.
  • a ball to powder weight ratio of 10: 1 was selected.
  • the milling experiments were carried out in an argon atmosphere for up to 200 hours.
  • Fig. 6 shows the X-ray diffraction of the powder obtained after different meals.
  • the Bragg reflections of the starting material decrease continuously as the meal increases, as indicated by the dashed line.
  • the Formation of the Mg 2 NiH 4 hydride phase becomes apparent after only 20 hours of milling.
  • the reaction is complete after 50 hours, the structure of the obtained hydride remains unchanged even with further grinding.
  • MgH 2 powder and elemental Ni powder are mixed in a molar ratio of 5: 1.
  • 40 g of this powder mixture was ground in a planetary ball mill (type Fritsch P5) at 230 revolutions / min, using a hardened chromium steel vial (with a volume of 250 ml) and balls (with a diameter of 10 mm).
  • the ball to powder weight ratio was 10: 1.
  • the milling experiments were carried out in an argon atmosphere over a period of up to 200 hours.
  • Fig. 7 shows the X-ray diffraction of the powder after different grinding times.
  • the Bragg reflections of the starting materials decrease with increasing milling time.
  • the Ni peaks disappear and the Mg 2 NiH 4 hydride is formed.
  • a Mg 2 NiH 4 / MgH 2 two- phase composite has been produced.
  • the structure of the two-phase composite hydride remains unchanged even after further grinding.
  • Fig. 8 shows the PCT (Pressure Concentration Temperature) diagram of the composite.
  • the two pressure plateaus which refer to the formation of Mg 2 NiH 4 and MgH 2 , can be clearly distinguished become.
  • the total hydrogen capacity of the composite is 5 wt.%.
  • Mg powder and MgH 2 are mixed in a molar ratio of 9: 1. Thereafter, this mixture is mixed with elemental Ni powder in a molar ratio of 2: 1. 40 g of this powder mixture is ground in a planetary ball mill (type Fritsch P5) at 230 revolutions / min using a hardened chromium steel vial (with a volume of 250 ml) and balls (with a diameter of 10 mm). A ball to powder weight ratio of 10: 1 was selected. The milling experiments were carried out in an argon atmosphere for up to 200 hours.
  • Fig. 9 shows an X-ray diffraction of the hydride at different meals.
  • the Bragg reflections of MgH 2 almost disappeared after only 5 grinding hours.
  • the Ni peaks also significantly decreased and formed new phases.
  • no Ni diffraction peaks become apparent after 200 hours of milling, and a Mg 2 NiH 0.3 / Mg 2 Ni biphasic composite is obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)

Abstract

In a process of producing nanocrystalline metal hydrides, an elemental metal hydride of a first kind is subjected to a mechanical milling process with at least one elemental metal or at least one additional metal hydride to produce an alloy hydride.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung nanokristalliner Metallhydride.The invention relates to a process for the preparation of nanocrystalline metal hydrides.

Es ist bekannt, daß auf der Basis von reversiblen Metallhydriden Wasserstoff-Speicher, sogenannte Hydridspeicher, gebildet werden können. Hierbei wird durch Wärmeabgabe der Speicher geladen, d.h. Wasserstoff wird durch Chemisorption gebunden und durch Wärmezufuhr wieder entladen. Wasserstoff-Speicher könnten somit hervorragenden Energiespeicher für mobile und/oder stationäre Anwendungen bilden, d.h. diese würden, da bei der Entladung der Wasserstoff-Speicher keine schädlichen Emissionen frei werden, in Zukunft ein beachtliches Speicherpotential bilden.It is known that hydrogen storage, so-called hydride storage, can be formed on the basis of reversible metal hydrides. In this case, the storage is charged by heat, ie hydrogen is bound by chemisorption and discharged by supplying heat again. Hydrogen storage could thus form excellent energy storage for mobile and / or stationary applications, ie they would, since the discharge of the hydrogen storage no harmful emissions are released, form a considerable storage potential in the future.

Gut geeignet für derartige Hydridspeicher sind sogenannte nanokristalline Hydride, die sich durch eine schnelle Wasserstoffaufnahme- und -abgabekinetik auszeichnen. Allerdings ist ihre Herstellung bislang sehr aufwendig. Bisher wurden dazu zunächst durch Hochenergiemahlen aus elementaren Komponenten oder Vorlegierungen nanokristalline Legierungen hergestellt, wobei die Mahldauern sehr lang sein können. In einem anschließenden Prozeßschritt wurden diese nanokristallinen Legierungen einer u.U. mehrstufigen Wärmebehandlung unter hohem Wasserstoffdruck unterzogen und auf diese Weise hydriert. Für viele Legierungen ist darüber hinaus eine mehrfache Be- und Entladung mit Wasserstoff notwendig, um die volle Kapazität zu erreichen.Well-suited for such hydride storage are so-called nanocrystalline hydrides, which are characterized by rapid hydrogen uptake and release kinetics. However, their production has so far been very expensive. Up to now, nanocrystalline alloys have been produced by high energy milling from elemental components or master alloys, whereby the grinding times can be very long. In a subsequent process step, these nanocrystalline alloys were u.U. subjected to multi-stage heat treatment under high hydrogen pressure and hydrogenated in this way. In addition, many alloys require multiple hydrogen loading and unloading to achieve full capacity.

Alternativ wurde versucht, die entsprechenden Hydride durch Mahlen unter Wasserstoffatmosphäre oder auf rein chemischem Wege zu synthetisieren. Dabei zeigte sich allerdings, daß die Ausbeute an den gewünschten Hydriden geringer ist und zum Teil zusätzliche unerwünschte Phasen auftreten.Alternatively, attempts have been made to synthesize the corresponding hydrides by milling under a hydrogen atmosphere or purely chemically. It was found, however, that the yield of the desired hydrides is lower and some additional undesirable phases occur.

T. N. Dymove et al, Coordination Chemistry, 1993, vol 19, no. 7, Seiten 529-534 offenbart die Herstellung von Hydriden von Aluminium und Alkalimetall, durch mechanische Mahlung von Aluminiumhydrid und Alkalimetallhydrid. Die Mahlung findet statt unter Argonatmosphäre. TN Dymove et al, Coordination Chemistry, 1993, vol. 19, no. 7, pp. 529-534 discloses the preparation of hydrides of aluminum and alkali metal by mechanical milling of aluminum hydride and alkali metal hydride. The grinding takes place under argon atmosphere.

Weiterhin sind bestimmte Phasen mit diesen konventionellen Methoden überhaupt nicht darstellbar.Furthermore, certain phases can not be represented with these conventional methods at all.

Es ist somit Aufgabe der vorliegenden Erfindung, ein Verfahren der eingangs genannten Art zu schaffen, mit dem eine Herstellung von stabilen und metastabilen Hydriden oder Hydriden metastabiler Legierungen erreicht werden kann, und zwar mit einer sehr hohen Ausbeute bis in den Bereich von 100 %, wobei das Verfahren unter verhältnismäßig einfach beherrschbaren Randbedingungen durchführbar sein soll und mit verhältnismäßig geringer Energiezufuhr betrieben werden kann.It is therefore an object of the present invention to provide a method of the type mentioned, with which a production of stable and metastable hydrides or hydrides of metastable alloys can be achieved, with a very high yield up to the range of 100%, wherein the method should be feasible under relatively simple controllable boundary conditions and can be operated with relatively low energy input.

Gelöst wird die Aufgabe gemäß der Erfindung dadurch, daß ein elementares Metallhydrid einer ersten Art mit wenigstens einem elementaren Metall zur Schaffung eines Legierungshydrids einem mechanischen Mahlvorgang unterworfen werden.The object is achieved according to the invention in that an elemental metal hydride of a first type with at least one elemental metal to provide an alloy hydride are subjected to a mechanical grinding process.

Der Vorteil der erfindungsgemäßen Lösung besteht im wesentlichen darin, daß, wie angestrebt, mit einer hohen Ausbeute bis in den Bereich von 100 % eine Herstellung von stabilen und metastabilen Hydriden oder Hydriden metastabiler Legierungen auf verhältnismäßig einfache Weise möglich ist und die Nachteile, die bei den im Stand der Technik bekannten Verfahren zur Herstellung von Hydrid-Speichern auftreten, vermieden werden, wobei mit dem erfindungsgemäßen Verfahren zudem auch Hydride hergestellt werden können, die mittels der bekannten Verfahren überhaupt nicht herstellbar sind.The advantage of the solution according to the invention consists essentially in that, as desired, with a high yield up to the range of 100%, a production of stable and metastable hydrides or hydrides of metastable alloys in a relatively simple manner is possible and the disadvantages associated with the In addition, with the process according to the invention, it is also possible to prepare hydrides which can not be prepared at all by means of the known processes.

Je nach den verwendeten Hydriden zur Herstellung nanokristalliner Metallhydride wird der Mahlvorgang des Gemisches aus elementarem Metallhydrid, Metall und eventuell mehreren weiteren Metallhydriden vorzugsweise eine vorbestimmte Zeit lang durchgeführt werden, wobei vorzugsweise der Mahlvorgang im Bereich von 20 bis 200 Stunden liegt.Depending on the hydrides used for the preparation of nanocrystalline metal hydrides, the grinding of the mixture of elemental metal hydride, metal and possibly several other metal hydrides is preferably carried out for a predetermined time, preferably the grinding process is in the range of 20 to 200 hours.

Grundsätzlich ist aber das Zeitintervall des Mahlvorgangs von der Bauart der verwendeten Mahleinrichtung abhängig, so daß die angegebenen, vorzugsweisen Mahldauern unter oder überschritten werden können. Allgemein kann aber gesagt werden, daß die erfindungsgemäßen Mahldauern deutlich kürzer als die beim Mahlen ohne Einsatz von Hydriden sind.Basically, however, the time interval of the milling process of the type of grinder used depends so that the specified, preferably grinding times can be under or exceeded. In general, however, it can be said that the grinding times according to the invention are significantly shorter than those during grinding without the use of hydrides.

Der Mahlvorgang findet unter einer Inertgasatmosphäre statt. Wie oben schon erwähnt, wurden bisher Hydride, beispielsweise Magnesium-Eisen-Hydrid, durch Sinterung bei hoher Temperatur und unter hohem Wasserstoffdruck hergestellt. Man hatte versucht, um bei diesem Beispiel zu bleiben, Magnesium und Eisen in einer Wasserstoffatmosphäre zu mahlen, dieses führte jedoch nicht zu einer Synthetisierung des gewünschten Magnesium-Eisen-Hydrids. Durch Mahlen von Magnesiumhydrid und Eisen in einem bestimmten Molverhältnis unter Inertgasatmosphäre ist es jedoch erfindungsgemäß möglich, am Ende des Mahlvorganges ein wasserstoffangereichertes Hydrid direkt zu synthetisieren, was insbesondere bei Verwendung von Argon als Inertgas sehr gute Erfolge gezeigt hat.The grinding process takes place under an inert gas atmosphere. As mentioned above, hitherto, hydrides, for example, magnesium iron hydride, have been produced by sintering at high temperature and under high hydrogen pressure. It had been tried to stay in this example to grind magnesium and iron in a hydrogen atmosphere, but this did not result in a synthesis of the desired magnesium iron hydride. By grinding magnesium hydride and iron in a certain molar ratio under an inert gas atmosphere, however, it is possible according to the invention to directly synthesize a hydrogen-enriched hydride at the end of the grinding process, which has shown very good results, in particular when using argon as an inert gas.

Besonders gute Ergebnisse wurden mit dem Verfahren vorzugsweise dadurch realisiert, daß das erste elementare Metallhydrid aus Metallen der I. oder II. Hauptgruppe des Periodensystems der Elemente besteht. Die Metalle sind vorzugsweise Li, Na, K, Mg, Ca, Sc, Y, Ti, V, Ny oder La, wobei die Elemente vorzugsweise Fe, Co, Nb, Cu, Zn, Al und Si sind. Besonders gute Verfahrensergebnisse wurden ebenfalls dadurch erreicht, daß vorzugsweise das elementare Metall aus Elementen der VIII. Nebengruppe des Periodensystems der Elemente besteht.Particularly good results were realized with the method preferably in that the first elemental metal hydride consists of metals of the 1st or 2nd main group of the Periodic Table of the Elements. The metals are preferably Li, Na, K, Mg, Ca, Sc, Y, Ti, V, Ny or La, which elements are preferably Fe, Co, Nb, Cu, Zn, Al and Si. Particularly good process results were also achieved in that preferably the elemental metal consists of elements of VIII. Subgroup of the Periodic Table of the Elements.

Die Metallhydride und/oder das Metall werden vorher in eine pulverförmige Form zu überführt und dann werden die pulverförmigen Metallhydride und/oder das Metall dem erfindungsgemäßen Mahlvorgang zu unterworfen. So ist das Verfahren effektiv betreibbar und infolgedessen mit einer extrem hohen Ausbeute betreibbar.The metal hydrides and / or the metal are previously converted into a powdery form and then the powdered metal hydrides and / or the metal are subjected to the grinding process according to the invention. Thus, the process is effectively operable and consequently operable with an extremely high yield.

Die Erfindung wird nun unter Bezugnahme auf die nachfolgenden schematischen Darstellungen anhand mehrerer Beispiele im einzelnen beschrieben. Darin zeigen:

Fig. 1
die Röntgenstrahlbeugung des Mg2FeH6-Pulvers,
Fig. 2
eine Bestätigung des Ergebnisses des Beispiels 1 durch Überprüfung mit einem Differential-Scanning-Kalorimeter DSC unter Wasserstoff,
Fig. 3
die Röntgenstrahlbeugung des Na3AlH6-Pulvers,
Fig. 4
eine Bestätigung des Ergebnisses des Beispiels von Fig. 3 durch Überprüfung mit einem Differential-Scanning-Kalorimeter DSC unter Wasserstoff,
Fig. 5
die Röntgenstrahlbeugung des Na2AlLiH6-Pulvers,
Fig. 6
die Röntgenstrahlbeugung des (MgH2)67Ni33-Pulvergemisches nach unterschiedlichen Mahlzeiten,
Fig. 7
die Röntgenstrahlbeugung des Mg2NiH4/MgH2-Pulvergemisches nach unterschiedlichen Mahlzeiten,
Fig. 8
das PCT-Diagramm des Mg2NiH4/MgH2-Zweiphasen-Kompositpulvers
Fig. 9
die Röntgenstrahlbeugung des (Mg-10 mol % MgH2)67Ni33-Pulvergemisches bei unterschiedlichen Mahlzeiten und
Fig. 10
der Vergleich der Wasserstoffabsorptionskinetik bei 300°C für Mg2Ni, berechnet mit unterschiedlichen Werten von MgH2.
The invention will now be described in detail with reference to the following schematic diagrams with reference to several examples. Show:
Fig. 1
the X-ray diffraction of the Mg 2 FeH 6 powder,
Fig. 2
confirmation of the result of Example 1 by checking with a differential scanning calorimeter DSC under hydrogen,
Fig. 3
X-ray diffraction of Na 3 AlH 6 powder,
Fig. 4
a confirmation of the result of the example of Fig. 3 by checking with a differential scanning calorimeter DSC under hydrogen,
Fig. 5
the X-ray diffraction of Na2AlLiH 6 powder,
Fig. 6
the X-ray diffraction of the (MgH 2 ) 67 Ni 33 powder mixture after different meals,
Fig. 7
the X-ray diffraction of the Mg 2 NiH 4 / MgH 2 powder mixture after different meals,
Fig. 8
the PCT diagram of the Mg 2 NiH 4 / MgH 2 two-phase composite powder
Fig. 9
the X-ray diffraction of the (Mg-10 mol% MgH 2 ) 67 Ni 33 powder mixture at different meals and
Fig. 10
Comparison of hydrogen absorption kinetics at 300 ° C for Mg 2 Ni, calculated with different values of MgH 2 .

Es ist bekannt, daß Magnesium und Eisen nicht mischbar sind. Der gewöhnliche Weg zur Herstellung von Hydriden war beispielsweise die Wärmebehandlung der Bestandteile, die zum gewünschten Hydrid führen sollen, und zwar bei sehr hoher Temperatur und bei hohem Wasserstoffgasdruck. Frühere Versuche ergaben, daß grundsätzlich das Mahlen von Magnesium und Eisen unter Wasserstoffatmosphäre nicht zu einer Synthetisierung beispielsweise eines Hydrids in Form von Mg2FeH6 führte. Diese Versuche hatten aber ergeben, daß das Mahlen der Bestandteile grundsätzlich eine Absenkung der Wärmebehandlungstemperatur und des Wasserstoffdrucks ermöglichte.It is known that magnesium and iron are immiscible. For example, the common way to prepare hydrides has been to heat treat the ingredients that are to produce the desired hydride at very high temperature and hydrogen gas pressure. Previous experiments showed that, in principle, milling magnesium and iron under a hydrogen atmosphere did not result in synthesizing, for example, a hydride in the form of Mg 2 FeH 6 . However, these experiments had shown that the grinding of the components basically allowed a lowering of the heat treatment temperature and the hydrogen pressure.

Beim erfindungsgemäßen Verfahren werden elementare Hydride und elementares Metall der Elemente der VIII. Nebengruppe des Periodensystems der Elemente, beispielsweise MgH2 und Fe, unter Argonatmosphäre gemahlen. Erfindungsgemäß wurde gefunden, daß es am Ende des Mahlvorganges möglich war, das entstandene Hydrid Mg2FeH6 ohne nachfolgendes Sintern direkt zu synthetisieren.In the process according to the invention elemental hydrides and elemental metal of the elements of VIII. Subgroup of the Periodic Table of the Elements, such as MgH 2 and Fe, are milled under an argon atmosphere. According to the invention it was found that it was possible at the end of the grinding process, the resulting hydride Mg 2 FeH 6 without subsequent sintering to synthesize directly.

Beispiel 1:Example 1: Synthetisierung von MgSynthesis of Mg 22 FeHFeH 66

Experimentelle Einzelheiten: 3 g von MgH2 und Fe in einem Molverhältnis von 2 : 1 werden innerhalb eines 60 ml-Tiegels mit drei Stahlkugeln (zwei mit 1,27 cm und einer mit 1,429 cm) angeordnet. Das Pulver wurde einer intensiven mechanischen Pulverisierung in einer hochenergetischen Kugelmahlmaschine des Typs SPEX 8000 (SPEX ist eine eingetragene Marke) unterworfen. Die Mahlung wurde unter Argonatmosphäre ausgeführt, und zwar 60 Stunden lang. Die in Fig. 1 dargestellte Röntgenstrahlbeugung des erhaltenen Mg2FeH6-Pulvers zeigt das synthetisierte Hydrid gemäß Beispiel 1. Das Ergebnis wurde bestätigt durch eine Untersuchung mit einem Differential-Scanning-Kalorimeter DSC unter Wasserstoff. Die Röntgenstrahlbeugung des Pulvers gemäß Beispiel 1 zeigte eine Kristallgröße des Mg2FeH6 von 22 nm.Experimental Details: 3 g of MgH 2 and Fe in a molar ratio of 2: 1 are placed inside a 60 ml crucible with three steel balls (two 1.27 cm and one 1.429 cm). The powder was subjected to intensive mechanical pulverization in a high-energy ball milling machine of the type SPEX 8000 (SPEX is a registered trademark). The milling was carried out under argon atmosphere for 60 hours. In the Fig. 1 The X-ray diffraction of the Mg 2 FeH 6 powder obtained shows the synthesized hydride according to Example 1. The result was confirmed by examination with a differential scanning calorimeter DSC under hydrogen. The X-ray diffraction of the powder according to Example 1 showed a crystal size of Mg 2 FeH 6 of 22 nm.

Beispiel 2 (Vergleichsbeispiel)Example 2 (comparative example) Synthetisierung von NaSynthesis of Na 33 AlHAlH 66

Experimentelle Einzelheiten: 3 g von NaH und NaAlH4 in einem Molverhältnis von 2 wurden in einen 60 ml-Tiegel zusammen mit 3 Stahlkugeln (zwei mit 1,27 cm und einer mit 1,429 cm) gegeben. Das Pulver wurde einer intensiven mechanischen Pulverisierung in einer hochenergetischen Mahlmaschine des Typs SPEX 8000 unterworfen. Das Mahlen wurde unter einer Argonatmosphäre 20 Stunden lang ausgeführt. Die Röntgenstrahlbeugung des in Fig. 3 dargestellten Pulvers zeigt die Formation von Na3AlH6 gemäß Beispiel 2. Dieses Ergebnis wurde bestätigt durch Überprüfung mit einem Differential-Scanning-Kalorimeter DSC unter Wasserstoff, vergleiche Fig. 4.Experimental details: 3 g of NaH and NaAlH 4 in a molar ratio of 2 were placed in a 60 ml crucible together with 3 steel balls (two by 1.27 cm and one by 1.429 cm). The powder was subjected to intensive mechanical pulverization in a high-energy SPEX 8000 milling machine. The milling was carried out under an argon atmosphere for 20 hours. The X-ray diffraction of in Fig. 3 The powder shown shows the formation of Na 3 AlH 6 according to Example 2. This result was confirmed by testing with a differential scanning calorimeter DSC under hydrogen, cf. Fig. 4 ,

Beispiel 3 (Vergleichsbeispiel)Example 3 (comparative example) Synthese von NaSynthesis of Na 22 AlLiHAlLiH 66

Experimentelle Einzelheiten: 3 g von NaH, LiH und NaAlH4 in einem Molverhältnis von 1 : 1 : 1 wurden in einen 60 ml-Tiegel mit 3 Stahlkugeln (zwei mit 1,27 cm und einer mit 1,429 cm) gegeben. Die Pulver wurde einer intensiven mechanischen Mahlung in einer hochenergetischen Kugelmahlmaschine des Typs SPEX 8000 unterworfen. Das Mahlen wurde unter einer Argonatmosphäre über eine Zeit von 40 Stunden ausgeführt. Die in Fig. 5 dargestellte Röntgenstrahlbeugung des Pulvers zeigt die Formation des Na2AlLiH6-Hydrids.Experimental details: 3 g of NaH, LiH and NaAlH 4 in a molar ratio of 1: 1: 1 were placed in a 60 ml crucible with 3 steel balls (two at 1.27 cm and one at 1.429 cm). The powders were subjected to intensive mechanical milling in a high-energy ball milling machine of the type SPEX 8000. The milling was carried out under an argon atmosphere over a period of 40 hours. In the Fig. 5 shown X-ray diffraction of the powder shows the formation of the Na 2 AlLiH 6 -Hydrids.

Beispiel 4:Example 4: Synthese von MgSynthesis of Mg 22 NiHNiH 44

Experimentelle Einzelheiten: MgH2-Pulver und elementares Ni-Pulver wurden in einem Molverhältnis von 2 : 1 gemischt. 40 g dieses Pulvergemisches wurden in einer Planetkugelmühle (Typ Fritsch P5) gemahlen, und zwar bei 230 Umdrehungen/min, wobei ein gehärteter Chromstahlbecher (mit einem Volumen von 250 ml) und Kugeln. (mit einem Durchmesser von 10 mm) benutzt wurden. Ein Kugel zu Pulver-Gewichtsverhältnis von 10 : 1 wurde ausgewählt. Die Mahlexperimente wurden bei einer Argonatmosphäre bis zu 200 Stunden ausgeführt.Experimental details: MgH 2 powder and elemental Ni powder were mixed in a molar ratio of 2: 1. 40 g of this powder mixture was ground in a planetary ball mill (type Fritsch P5), at 230 revolutions / min, with a hardened chrome steel cup (with a volume of 250 ml) and balls. (with a diameter of 10 mm) were used. A ball to powder weight ratio of 10: 1 was selected. The milling experiments were carried out in an argon atmosphere for up to 200 hours.

Fig. 6 zeigt die Röntgenstrahlbeugung des Pulvers, das nach unterschiedlichen Mahlzeiten erhalten wurde. Die Bragg'schen Reflexionen des Ausgangsmaterials nehmen kontinuierlich mit der Zunahme der Mahlzeit ab, was durch die gestrichelte Linie dargestellt ist. Die Formation der Mg2NiH4-Hydridphase wird schon nach 20 Stunden des Mahlens erkennbar. Die Reaktion ist nach 50 Stunden abgeschlossen, wobei der Aufbau des erhaltenen Hydrids auch bei weiterem Mahlen unverändert bleibt. Fig. 6 shows the X-ray diffraction of the powder obtained after different meals. The Bragg reflections of the starting material decrease continuously as the meal increases, as indicated by the dashed line. The Formation of the Mg 2 NiH 4 hydride phase becomes apparent after only 20 hours of milling. The reaction is complete after 50 hours, the structure of the obtained hydride remains unchanged even with further grinding.

Beispiel 5:Example 5: Synthetisierung eines MgSynthesizing a Mg 22 NiHNiH 44 /MgH/ MgH 22 (Mg(Mg 8383 NiNi 1717 )-Gemisches unter Verwendung von MgH) Mixture using MgH 22

Experimentelle Einzelheiten: MgH2-Pulver und elementares Ni-Pulver werden in einem Molverhältnis 5 : 1 gemischt. 40 g dieser Pulvermischung wurde in einer Planetkugelmühle (Typ Fritsch P5) bei 230 Umdrehungen/min gemahlen, wobei eine gehärtete Chromstahlphiole (mit einem Volumen von 250 ml) und Kugeln (mit einem Durchmesser von 10 mm) verwendet wurden. Als Kugel zu Pulver-Gewichtsverhältnis wurde 10 : 1 ausgewählt. Die Mahlexperimente wurden in einer Argonatmosphäre über eine Zeit von bis zu 200 Stunden ausgeführt.Experimental details: MgH 2 powder and elemental Ni powder are mixed in a molar ratio of 5: 1. 40 g of this powder mixture was ground in a planetary ball mill (type Fritsch P5) at 230 revolutions / min, using a hardened chromium steel vial (with a volume of 250 ml) and balls (with a diameter of 10 mm). The ball to powder weight ratio was 10: 1. The milling experiments were carried out in an argon atmosphere over a period of up to 200 hours.

Fig. 7 zeigt die Röntgenstrahlbeugung des Pulvers nach unterschiedlichen Mahldauern. Die Bragg'schen Reflexionen der Ausgangsmaterialien nehmen ab mit zunehmender Mahldauer. Nach 100 Stunden des Mahlens sind die Ni-Peaks verschwunden und das Mg2NiH4-Hydrid ist ausgebildet. Auf diese Weise ist ein Mg2NiH4/MgH2-Zweiphasenkomposit erzeugt worden. Der Aufbau des zweiphasigen Komposithydrids verbleibt auch nach weiterem Mahlen unverändert. Fig. 7 shows the X-ray diffraction of the powder after different grinding times. The Bragg reflections of the starting materials decrease with increasing milling time. After 100 hours of milling, the Ni peaks disappear and the Mg 2 NiH 4 hydride is formed. In this way, a Mg 2 NiH 4 / MgH 2 two- phase composite has been produced. The structure of the two-phase composite hydride remains unchanged even after further grinding.

Fig. 8 zeigt das PCT (Pressure-Concentration-Temperature) -Diagramm des Komposits. Die beiden Druckplateaus, die sich auf die Bildung des Mg2NiH4 und MgH2 beziehen, können klar unterschieden bzw. auseinandergehalten werden. Die Gesamtwasserstoffkapazität des Komposits beträgt 5 wt.%. Fig. 8 shows the PCT (Pressure Concentration Temperature) diagram of the composite. The two pressure plateaus, which refer to the formation of Mg 2 NiH 4 and MgH 2 , can be clearly distinguished become. The total hydrogen capacity of the composite is 5 wt.%.

Beispiel 6:Example 6: Synthese von MgSynthesis of Mg 22 NiHNiH 0,30.3 //Mg// Mg 22 Ni-Komposit unter Verwendung von 10 mol% MgHNi composite using 10 mol% MgH 22 und 90 mol% Mgand 90 mol% Mg

Experimentelle Einzelheiten: Mg-Pulver und MgH2 werden in einem Molverhältnis von 9 : 1 gemischt. Danach wird dieses Gemisch mit elementarem Ni-Pulver in einem Molverhältnis von 2 : 1 gemischt. 40 g dieses Pulvergemisches wird in einer Planetkugelmühle (des Typs Fritsch P5) bei 230 Umdrehungen/min gemahlen, wobei eine gehärtete Chromstahlphiole (mit einem Volumen von 250 ml) und Kugeln (mit einem Durchmesser von 10 mm) verwendet wurden. Ein Kugel zu Pulver-Gewichtsverhältnis von 10 : 1 wurde ausgewählt. Die Mahlexperimente wurden in einer Argonatmosphäre bis zu 200 Stunden ausgeführt.Experimental details: Mg powder and MgH 2 are mixed in a molar ratio of 9: 1. Thereafter, this mixture is mixed with elemental Ni powder in a molar ratio of 2: 1. 40 g of this powder mixture is ground in a planetary ball mill (type Fritsch P5) at 230 revolutions / min using a hardened chromium steel vial (with a volume of 250 ml) and balls (with a diameter of 10 mm). A ball to powder weight ratio of 10: 1 was selected. The milling experiments were carried out in an argon atmosphere for up to 200 hours.

Fig. 9 zeigt eine Röntgenstrahlbeugung des Hydrids bei unterschiedlichen Mahlzeiten. Die Bragg'schen Reflexionen des MgH2 sind nach lediglich 5 Mahlstunden nahezu verschwunden. Nach einer Mahlzeit von 20 Stunden haben sich die Ni-Peaks ebenso signifikant vermindert und neue Phasen gebildet. Schließlich sind keine Ni-Beugungspeaks mehr ersichtlich nach 200 Mahlstunden und ein Mg2NiH0,3/Mg2Ni zweiphasiges Komposit wird erhalten. Fig. 9 shows an X-ray diffraction of the hydride at different meals. The Bragg reflections of MgH 2 almost disappeared after only 5 grinding hours. After a 20-hour meal, the Ni peaks also significantly decreased and formed new phases. Finally, no Ni diffraction peaks become apparent after 200 hours of milling, and a Mg 2 NiH 0.3 / Mg 2 Ni biphasic composite is obtained.

Die kinetischen Eigenschaften der in den Beispielen 4 und 6 während des ersten Absorptionszyklusses (nach der anfänglichen Desorption) beschriebenen Materialien werden mit den Eigenschaften von M92Ni verglichen, die aus den reinen Materialien, vergleiche Fig. 10, hergestellt worden sind. Während das Mg2NiH0,3/Mg2Ni-Zweiphasengemisch lediglich eine minimale Verbesserung im Hinblick auf das Material darstellt, das ohne MgH2 gemahlen worden ist, ist das Mg2NiH4, das mit 100 % MgH2 gemahlen worden ist, klar das bessere und absorbiert Wasserstoff bis zu 80 % der Gesamtkapazität innerhalb von 20 Sekunden.The kinetic properties of the materials described in Examples 4 and 6 during the first absorption cycle (after initial desorption) are compared with the properties of M 92 Ni, which is made from the pure materials Fig. 10 , have been produced. While the Mg 2 NiH 0.3 / Mg 2 Ni two-phase mixture As a minimal improvement in material milled without MgH 2 , the Mg 2 NiH 4 milled with 100% MgH 2 is clearly the better and absorbs hydrogen up to 80% of the total capacity within 20 seconds.

Claims (6)

  1. A process for manufacturing nanocrystalline metal hydrides, wherein at least one elemental metal hydride is subjected to a mechanical milling process together with at least one elemental metal under an inter gas atmosphere for the production of an alloy hydride, whereby the at least one elemental metal hydride and the metal are supplied to the milling process in the form of a powder.
  2. Process according to claim 1, characterized in that the duration of the milling process is in the region of from 20 to 200 hours.
  3. Process according to any of the preceding claims, characterized in that the inert gas is argon.
  4. Process according to any of the preceding claims, characterized in that the elemental metal hydride consists of metals of the I. or III. main group of the periodic system of the elements.
  5. Process according to any of the preceding claims, characterized in that the elemental metal consists of elements of the VIII. sub-group of the periodic system of the elements.
  6. Process according to any of the preceding claims, characterized in that a further metal hydride consists of a mixture of elements of the I. and III. main group of the periodic system of the elements.
EP98966570A 1997-12-23 1998-12-22 Process for preparing nanocrystalline metal hydrides Expired - Lifetime EP1042218B1 (en)

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